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系統識別號 U0002-1308200914285300
中文論文名稱 3-雙苯咪唑取代聯吡啶釕錯合物之合成及性質研究
英文論文名稱 Synthesis and Characterizations of Ru(II) Complex with 3, 3’-Dibenzimidazole-2, 2’-bipyridine
校院名稱 淡江大學
系所名稱(中) 化學學系碩士班
系所名稱(英) Department of Chemistry
學年度 97
學期 2
出版年 98
研究生中文姓名 彭松崑
研究生英文姓名 Sung-Kun Peng
學號 696160604
學位類別 碩士
語文別 中文
口試日期 2009-07-16
論文頁數 65頁
口試委員 指導教授-王文竹
委員-林志彪
委員-張一知
中文關鍵字 釕金屬  苯咪唑  聯吡啶  氟離子偵測 
英文關鍵字 ruthenium  benzimidazole  bipyridine  F sensing 
學科別分類 學科別自然科學化學
中文摘要 我們合成出在聯吡啶3,3’位置苯咪唑取代之配位子,並將配位子與RuII(bp)2Cl2反應,得到釕錯合物[Ru(3-dbimbp)(bpy)2](PF6)2,利用核磁共振光譜、質譜及X-ray晶體解析來鑑定化合物的結構,利用電子吸收光譜、發射光譜及電化學來探討其物理及化學性質。
[Ru(3-dbimbp)(bpy)2](PF6)2的單晶結構中,釕金屬與聯吡啶的氮原子形成六配位的八面體形狀,苯咪唑未參與配位,配位子以聯吡啶與金屬配位的方式,我們是第一個發現的。配位子3-dbimbp的發射光譜中,有屬於TICT的發光。釕錯合物的紫外光-可見光光譜中,有配位子、聯吡啶的π-π*電子躍遷及MLCT吸收峰。發射光譜中,660 nm有一放射峰,此為來自於MLCT激態的磷光。電化學實驗中,有一組RuII/RuIII氧化還原峰在1.54 V,在還原部份,有四組不可逆的氧化還原峰(-1.06 V、-1.35 V、-1.54 V、-1.78 V),分別來自於配位子及聯吡啶。
在氟離子滴定實驗中,配位子及錯合物在吸收光譜及發射光譜皆有顯著的變化,酸鹼滴定的實驗中,發現[OH-]與氟離子的表現相似,此結果顯示配位子與錯合物是受到了去質子化的影響。在其他陰離子(Cl-, Br-, I-, ClO4-, HSO4-, NO3-)滴定實驗中,並沒有偵測效果,故我們所合成出的配位子及錯合物對於氟離子有選擇性。
英文摘要 A new polypyridyl ruthenium complex, [Ru(3-dbimbp)(bpy)2](PF6)2 , containing two bipyridines and one bipyridine derivative ligand 3-dbimbp (3-dbimbp = 3,3'-dibenzimidazole-2,2'-bipyridine) was synthesized. Mass, NMR, UV-vis and Emission spectrometer are employed to study the structure of this complex. Single crystal x-ray diffraction structure of [Ru(3-dbimbp)(bpy)2](PF6)2 was obtained. Electronic absorption and emission spectra of this complex are measured to investigate the electronic structure of the complex. A strong absorption is assigned as intraligand π-π* transition and the strong absorption is attributed to an MLCT transition. However, emission spectra exhibit photoluminescence, which has been attributed to MLCT triplet emission. The cyclic voltammogram was measured, showing a metal-centered RuII/RuIII oxidation with potentials at 1.54V.
The results of absorption and emission spectra revealed that the ligand and complex can be employed as a sensor for fluoride anion. Finally, a proposed deprotonation mechanism for sensing fluoride anion was discussed.
論文目次 目錄
中文摘要
英文摘要
第一章 緒論
1-1多吡啶釕錯合物系統…………………………………………….1
1-2 過渡金屬錯合物酸鹼性質與發光性質…………………………2
1-3多吡啶配位子…………………………………………………….3
1-4釕金屬錯合物的應用…………………………………………….3
1-5實驗設計………………………………………………………….7

第二章 實驗部份
2-1藥品……………………………………………………...………..8
2-2 物理測定儀器.................................................................................8
2-3 配位子的合成…………………………………………………...10
2-4 釕錯合物的合成………………………………………………...12

第三章 結果與討論
3-1. 化合物的合成與結構…………………………………………..13
3-1-1 配位子的合成與鑑定………………………...…………….13
3-1-2 錯合物的合成與鑑定……………………………………....14
3-2 錯合物的晶體結構…..………………………………………….16
3-3 電子光譜性質…………………………………………………...20
3-3-1 配位子的電子吸收光譜…………………………………....20
3-3-2 錯合物的電子吸收光譜…………………………………....20
3-3-3 配位子的發射光譜……………………………………...….23
3-3-4 錯合物的發射光譜………………………………………....24
3-3-5 量子產率 ( Quantum yield )……………………………….26
3-3-6 配位子的生命期………….………………………………...28
3-3-7 錯合物的生命期……………………….…………………..28
3-4. 錯合物的電化學性質…………………………………………..30
3-5 酸鹼性質………………….……………………………………..34
3-5-1 配位子鹼滴定的吸收光譜…………………………...…….34
3-5-2 配位子鹼滴定的發射光譜..………………………………..35
3-5-3 錯合物鹼滴定的吸收光譜………………………………....37
3-5-4 錯合物鹼滴定的發射光譜……………………………...….38
3-6 氟離子的感測…………………………………………………...40
3-6-1 配位子的陰離子偵測……………………………………....40
3-6-2 錯合物的陰離子偵測……………………...……………….46

第四章 結論…………………………………………………..56
第五章 參考資料……………………………………………..57

附錄………..…………………………………………………..59

圖目錄
Figure 1.1 Ground- and Excited-State Acid-Base Equilibrium……………………….1
Figure 1.2 Representation of Ru complex, a luminescent pH sensor through protonation and deprotonation……..……………………………………...4
Figure 1.3 Ruthenium complex had crown ether subtitled group for cation sensing…5
Figure 1.4 Ruthenium complex had urea subtitled group for anion sensing………….6
Figure 1.5 Ruthenium complexes had phenol and catechol subtitled group for anion sensing……………………………………..………………………………6
Figure 1.6 Ruthenium complexes had imidazole subtitled group for anion sensing….7
Figure 3.1 The NMR spectrum of 3-dbimbp in d6-DMSO…………………………..13
Figure 3.2 Electrospray ionization mass spectrum of [Ru(3-dbimbp)(bpy)2](PF6)….14
Figure 3.3 Isotope pattern of [Ru(3-dbimbp)(bpy)2-1H]+ on m/z = 801……………..15
Figure 3.4 ORTEP diagram of [Ru(3-dbimbp)(bpy)2](PF6)2 with 50% thermal ellipsoids. The hydrogen atoms, counter anions (PF6-) and solvent molecules are omitted for clarity…………………………………………16
Figure 3.5 X-ray structures of [Ru(3-dbimbp)(bpy)2](PF6)2 viewing from a-axis and c-axis ..…………………………………………………………………….17
Figure 3.6 UV-vis spectrum for 3-dbimbp in methanol……………………………...20
Figure 3.7 UV-vis spectra for 3-dbimbp and [Ru(3-dbimbp)(bpy)2(PF6)2] in methanol
………………………………………………………………………...….21
Figure 3.8 UV-vis spectra for Ru(bpy)3 and Ru(3-dbimbp)(bpy)2(PF6)2 in methanol
……………………………………………………………………..……..22
Figure 3.9 Electronic properties of ligand 3-dbimbp in methanol……………...……23
Figure 3.10 Electronic properties of Ru(3-dbimbp)(bpy)2(PF6)2 in methanol……….24
Figure 3.11 Emission spectra of Ru(bpy)3 and Ru(3-dbimbp)(bpy)2 in CH3CN (ex.480 nm).............................................................................................................25
Figure 3.12 Absorption spectra of Ru(bpy)3(PF6)2 and Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN……..………………………………………………….…………27
III
Figure 3.13 Emission spectra of Ru(bpy)3(PF6)2 and Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN (λex = 480 nm)……………………………………….…………..27
Figure 3.14 Life time of ligand 3-dbimbp in methanol………………………………28
Figure 3.15 Life time of Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN……………………..29
Figure 3.16 Cyclic voltammogram of Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN with 0.01 M TBAPF6 as the supporting electrolyte under nitrogen. scan rate : 100 mV/s;working electrode : glassy carbon;counter electrode : Pt rod;scanning range : (a) 2.0 V to -2.2 V (b) 0.0 V to -2.2 V………………….31
Figure 3.17 Cyclic voltammogram of 3-dbimbp in DMSO with 0.01 M TBAPF6 as the supporting electrolyte under nitrogen. scan rate : 100 mV/s;working electrode : glassy carbon;counter electrode : Pt rod…………………..31
Figure 3.18 Square wave voltammogram of Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN.
……………………………………………………………………..……32
Figure 3.19 UV-vis titration of 3-dbimbp in DMSO solution ( 5.2 × 10-5 M ) upon addition of [Bu4N]OH (0-3.31 equiv.)…………………………...………34
Figure 3.20 Corresponding titration profile for UV-vis titration upon addition of [Bu4N]OH………………………………………………………...………35
Figure 3.21 Emission titration of 3-dbimbp in DMSO solution ( 5.2 × 10-5 M ) upon addition of [Bu4N]OH (0-3.31 equiv.)…………………………...……..36
Figure 3.22 Corresponding titration profile for Emission titration upon addition of [Bu4N]OH……………………………………………………………….36
Figure 3.23 UV-vis titration of Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5.2 × 10-5 M ) upon addition of [Bu4N]OH (0-2.70 equiv.)…………...……….37
Figure 3.24 Corresponding titration profile for UV-vis titration upon addition of [Bu4N]OH…………………………………………………….…………38
Figure 3.25 Emission titration of Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5.2 × 10-5 M ) upon addition of [Bu4N]OH (0-2.70 equiv.)………………….39
Figure 3.26 Corresponding titration profile for Emission titration upon addition of [Bu4N]OH……………………………………………………………….39
IV
Figure 3.27 UV-vis titration of 3-dbimbp in DMSO solution ( 5 × 10-5 M ) upon addition of [Bu4N]F (0 -5.0 equiv.)……………………………………..40
Figure 3.28 Corresponding titration profile for UV-vis titration upon addition of [Bu4N]F…………………………………………………………………..41
Figure 3.29 Emission titration of 3-dbimbp in DMSO solution ( 5 × 10-5 M ) upon addition of [Bu4N]F (0-5.0 equiv.)……………………………………...41
Figure 3.30 Corresponding titration profile for emission titration upon addition of [Bu4N]F…………………………………………………………………..42
Figure 3.31 UV-vis titration and emission spectra for 3-dbimbp in DMSO solution ( 5 × 10-5 M ) upon addition of [Bu4N]Cl ( 0-5 equiv )…………...……….43
Figure 3.32 UV-vis titration and emission spectra for 3-dbimbp in DMSO solution ( 5 × 10-5 M ) upon addition of [Bu4N]Br ( 0-5 equiv )……………..……44
Figure 3.33 UV-vis titration and emission spectra for 3-dbimbp in DMSO solution ( 5 × 10-5 M ) upon addition of [Bu4N]I ( 0-5 equiv )…………………….44
Figure 3.34 UV-vis titration and emission spectra for 3-dbimbp in DMSO solution ( 5 × 10-5 M ) upon addition of TEAClO4 ( 0-6 equiv )………….………..45
Figure 3.35 UV-vis titration and emission spectra for 3-dbimbp in DMSO solution ( 5 × 10-5 M ) upon addition of TBAHSO4 ( 0-4.4 equiv )………………...45
Figure 3.36 UV-vis titration and emission spectra for 3-dbimbp in DMSO solution ( 5 × 10-5 M ) upon addition of TBANO3 ( 0-4.2 equiv )………………….46
Figure 3.37 UV-vis titration of Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5 × 10-5 M ) upon addition of [Bu4N]F (0-4.0 equiv)…………..…………47
Figure 3.38 Corresponding titration profile for UV-vis titration upon addition of [Bu4N]F…………………………………………………...…………….48
Figure 3.39 Emission titration of Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5 × 10-5 M ) upon addition of [Bu4N]F (0-4.0 equiv)…….……………….48
Figure 3.40 Corresponding titration profile for emission titration upon addition of [Bu4N]F ………………………………………………………..……....49
Figure 3.41 Life time of (a) Ru(3-dbimbp)(bpy)2(PF6)2 (b) addition of excess F- in CH3CN…………………………………...…………………………......51
Figure 3.42 UV-vis titration and emission spectra for Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5 × 10-5 M ) upon addition of [Bu4N]Cl (0-11 equiv).
………………………………………………………………..…………52
Figure 3.43 UV-vis titration and emission spectra for Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5 × 10-5 M ) upon addition of [Bu4N]Br (0-11 equiv).
…………………………………………………………………………..52
Figure 3.44 UV-vis titration and emission spectra for Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5 × 10-5 M ) upon addition of [Bu4N]I (0-11 equiv).
……………………………………………..……………………………53
Figure 3.45 UV-vis titration and emission spectra for Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5 × 10-5 M ) upon addition of TEAClO4 (0-11 equiv).
…………………………………………………………………………..53
Figure 3.46 UV-vis titration and emission spectra for Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5 × 10-5 M ) upon addition of [Bu4N]HSO4 (0-11 equiv)…………………..……………………………………………….54
Figure 3.47 UV-vis titration and emission spectra for Ru(3-dbimbp)(bpy)2(PF6)2 in CH3CN solution ( 5 × 10-5 M ) upon addition of [Bu4N]HSO4 (0-11 equiv)……………………………………………………………………54
Table 1. Crystal data and structure refinement for [Ru(3-dbimbp)(bpy)2](PF6)2 …....18
Table 2. Selecte bond lengths [Å] and angles [°] for [Ru(3-dbimbp)(bpy)2](PF6)2 ….19
Table 3. Electrochemical data for 3-dbimbp and ruthenium complexes……………..33
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